Ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids

ABSTRACT

Disclosed are ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids. The salts are surface active agents which are useful in a variety of applications as primary and/or secondary surfactants. The salts are especially useful as surfactants in emulsion polymerization reactions.

RELATED APPLICATIONS

This is a continuation-in-part of application Ser. No. 10/341,007, filedJan. 13, 2003, now abandoned, which is a continuation of applicationSer. No. 09/801,943, filed Mar. 8, 2001, now issued as U.S. Pat. No.6,506,804, which is a continuation of application Ser. No. 09/060,238,filed Apr. 14, 1998, abandoned, which is a continuation of applicationSer. No. 08/790,360, filed Jan. 28, 1997, abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel ethylenically unsaturated aminesalts of sulfonic, phosphoric and carboxylic acids. More specifically,the invention relates to ethylenically unsaturated amine salts ofalkylbenzene sulfonic acids, alkyl olefin sulfonic acids, alkyl alcoholsulfuric acid esters and alkoxylated alkyl alcohol sulfuric acid esters,and mixtures thereof. Additionally, the invention relates toethylenically unsaturated amine salts of alkyl carboxylic acids andalkyl phosphoric acids. The salts are polymerizable, surface activeagents which are useful in a variety of applications, especially indetergent formulations and in emulsion polymerization processes.

2. Description of the Related Art

Detergents, shampoos, cleansers, soaps, and the like, are used toperform a wide variety of household and industrial cleaning operationsand are formulated to give compositions which produce optimumperformance under the contemplated end use conditions. Typically, thesecompositions contain a variety of surface active agents known to theart, in the form of anionic, nonionic, amphoteric, and/or cationicsurfactants. The anionic surfactants used in the compositions aretypically in the form of alkali metal (lithium, sodium, potassium),alkaline earth (calcium, magnesium), ammonium and/or alkanolamine saltsof the corresponding anionic acid. In formulating such compositions, itis desirable to have a variety of surface active agents available forproducing and optimizing the compositions.

Surface active agents also find use in applications beyond typicaldetergent or shampoo formulations. For example, in a conventionalemulsion polymerization of ethylenically unsaturated monomers, one ormore surfactants are used to emulsify the monomers and the resultingpolymer products, i.e., latexes. The monomers used in emulsionpolymerization reactions are generally water-insoluble, but may also bewater-soluble. During the polymerization, small portions of monomer aresuspended in a continuous aqueous phase. Typically, a water solublesurfactant is present within the aqueous phase to aid in the suspensionof the monomer, with subsequent polymerization via a free-radicalpolymerization. The water soluble surface active agents, i.e.,surfactants, utilized in emulsion polymerization reactions are typicallyanionic, nonionic, cationic, or zwitterionic surfactants or mixturesthereof.

In a traditional emulsion polymerization reaction, discrete, solidpolymeric particles are formed during the course of the reaction to forma polymer product latex. Typically, the surfactant employed in such atraditional emulsion polymerization reaction does not react with, i.e.,become chemically bonded via carbon-carbon bond formation, the discretepolymeric particles. Rather, the surfactant remains unreacted in thepolymer product latex after the emulsion polymerization reaction iscomplete. The unreacted surfactant can interfere with the performance ofsuch polymerization products in coating, adhesive, sealant and elastomer(CASE) applications, non-woven fiber applications and carpet backings.The unreacted surfactant may cause pealing of a latex paint coating, anddecreased moisture resistance and scrubability resistance in variousCASE applications. Additionally, residual surfactant can cause anundesirable “blooming” that leads to surface irregularities in aresulting CASE that is applied to a substrate.

Several proposals have been made in the prior art to employ apolymerizable surfactant as the surface active agent during an emulsionpolymerization reaction. U.S. Pat. No. 5,478,883 (incorporated herein byreference) describes the use of ethylenically unsaturated polymerizablewater-soluble nonionic surfactants formed by the reaction of adiallylamine compound with ethylene oxide, propylene oxide or butyleneoxide, in emulsion polymerization reactions. Similarly, U.S. Pat. No.5,162,475 (incorporated herein by reference) provides alpha-betaethylenically unsaturated poly(alkylenoxy) polymerizable surface activecompounds for use in emulsion polymerization. For additional examples ofpolymerizable surfactants for use in emulsion polymerization processes,see U.S. Pat. Nos. 4,377,185 and 4,049,608.

SUMMARY OF THE INVENTION

The present invention provides ethylenically unsaturated amine salts ofsulfonic, phosphoric or carboxylic acids, or mixtures thereof. The aminesalts of the present invention are polymerizable, surface active agentssuitable for use as primary or secondary surfactants, and/or assurfactants in emulsion polymerization reactions.

Accordingly, the present invention provides novel ethylenicallyunsaturated amine salts of sulfonic, phosphoric or carboxylic acids, ormixtures thereof, which are polymerizable, surface active agents in avariety of applications. It has been discovered that these surfaceactive agents are useful, for example, in detergents (e.g., laundrydetergents, dish detergents, automatic dishwasher detergents, etc.),shampoos, 2-in-1 shampoos, 3-in-1 shampoos, cleansers, soaps, liquidhand soaps, body washes, agricultural herbicide and pesticideformulations and the like. Additionally, the surface active agents ofthe present invention are especially useful in emulsion polymerizationreactions and are generally capable of polymerizing with themselvesand/or co-polymerizing with other ethylenically unsaturated. monomers ofthe type which are commonly employed in emulsion polymerizationreactions.

The surface active agents of the present invention are prepared fromreadily available, economical raw materials, and generally, theirpreparation does not require any special handling or equipment. Thepolymerizable surface active agents may be prepared in a batch mode or acontinuous mode; they may be prepared by contacting the ethylenicallyunsaturated amine with the acid or contacting the acid with theethylenically unsaturated amine. By contacting it is meant that theacid(s) is added to the ethylenically unsaturated amine(s) and thecomponents are mixed, or the ethylenically unsaturated amine(s) is addedto the acid(s) and the components are mixed. Typically, the acid ispresent as an anion and the base is present as a cation (i.e. aquaternary nitrogen) in the mixture. The acid and nitrogenous base formsalts or quaternary nitrogen compounds. As known by one skilled in theart, upon mixing the acid and nitrogenous base together, the nitrogenousbase becomes a conjugate acid and the acid becomes a conjugate base.These polymerizable surface active agents are made by acid-basetitration reactions. These reactions are intended to have close to 100%yield, and should not result in significant byproducts.

The surface active agents and blends of surface active agents may beprepared in a variety of forms, including but not limited to, liquids,solutions, solids, powders, flakes, semi-solids, gels, “ringing” gels,G-phase liquids, hexagonal phase solids, or thick pastes. The surfaceactive agents may be spray dried, flaked, extruded, and the like.Although not critical to the present invention, the polymerizable,surface active agents may be prepared “neat” or in a conventionalsolvent such as water, low molecular weight alcohol or hydrocarbon, or amixture thereof, to produce an aqueous solution of the surface activeagent. The present invention encompasses surface active agents as saltsin dry form and as aqueous solutions. Salts of the surface active agentsmay be isolated by drying a solution of the surface active agents; asolution of surface active agents may be prepared by dissolving the saltof the surface active agent in water, low molecular weight alcohol orhydrocarbon, or a mixture thereof.

Individual surface active agents of the present invention may beprepared and mixed together to produce a surface active mixturecomprising “neat” surface active agents or an aqueous surfactant blend.Additionally, neat or aqueous blends of the surface active agents may beprepared by contacting a blend of two or more ethylenically unsaturatedamines with one acid, or by contacting a blend of two or moreethylenically unsaturated amines with a blend of 2 or more acids.Conversely, blends of the surface active agents may be prepared bycontacting a blend of two or more acids with one ethylenicallyunsaturated amine, or by contacting a blend of two or more acids with ablend of two or more ethylenically unsaturated amines.

These and other advantages of the present invention will be apparentfrom the following description of the invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention encompasses polymerizable, surface active agentswhich are salts or quaternary nitrogen compounds comprising:

-   -   a) at least one acid, wherein the acid is a sulfonic acid, a        carboxylic acid, or a phosphoric acid, or mixtures thereof; and    -   b) at least one nitrogenous base, wherein the nitrogenous base        contains at least one nitrogen atom and at least one        ethylenically unsaturated moiety.

The polymerizable surface active agents of the present invention aresalts or quaternary nitrogen compounds comprising at least one acid,wherein the acid is a sulfonic acid, a carboxylic acid, or a phosphoricacid, or a mixture thereof, and at least one nitrogenous base, whereinthe nitrogenous base contains at least one nitrogen atom and at least onethylenically unsaturated moiety. In general, although not required, thepolymerizable surface active agents have a homophilic/lipophilic balance(HLB) of less than about 45. In a somewhat more preferred embodiment,the polymerizable surface active agents have an HLB of about 5-40. Thepolymerizable surface active agents are generally capable ofpolymerization with themselves, co-polymerization with the ethylenicallyunsaturated monomer, or co-polymerization with a partially polymerizedpolymer.

More specifically, while the nitrogenous base may be capable of somedegree of surface activity, in the present invention it is the acidportion of the polymerizable surfactant that is responsible for thesurfactant character of the compound. In preferred embodiments, thenitrogenous base contributes little or no surfactant character to thesematerials. In other words, the acids are generally capable of acting assurfactants when they are present as anions of the acid and theassociated counterion is any positively charged species. The most commonpositively charged species are sodium, potassium, ammonium, calcium andmagnesium ions. In fact, the acid portion of the polymerizablesurfactant may be supplied as a sodium, potassium, or other salt of thecarboxylic, phosphoric or sulfonic acid and then combined with thenitrogenous base to form the inventive surfactant.

The acids useful in the present invention are generally sulfonic acids,polysulfonic acids, sulfonic acids of oils, paraffin sulfonic acids,lignin sulfonic acids, petroleum sulfonic acids, tall oil acids, olefinsulfonic acids, hydroxyolefin sulfonic acids, polyolefin sulfonic acids,polyhydroxy polyolefin sulfonic acids, carboxylic acids, perfluorinatedcarboxylic acids, carboxylic acid sulfonates, alkoxylated carboxylicacid sulfonic acids, polycarboxylic acids, polycarboxylic acidpolysulfonic acids, alkoxylated polycarboxylic acid polysulfonic acids,phosphoric acids, alkoxylated phosphoric acids, polyphosphoric acids,and alkoxylated polyphosphoric acids, fluorinated phosphoric acids,phosphoric acid esters of oils, phosphinic acids, alkylphosphinic acids,aminophosphinic acids, polyphosphinic acids, vinyl phosphinic acids,phosphonic acids, polyphosphonic acids, phosphonic acid alkyl esters,α-phosphono fatty acids, oragnoamine polymethylphosphonic acids,organoamino dialkylene phosphonic acids, alkanolamine phosphonic acids,trialkyledine phosphonic acids, acylamidomethane phosphonic acids,alkyliminodimethylene diphosphonic acids, polymethylene-bis(nitrilodimethylene)tetraphosphonic acids, alkyl bis(phosphonoalkylidene) amineoxide acids, esters of substituted aminomethylphosphonic acids,phosphonamidic acids, acylated amino acids (e.g., amino acids reactedwith alkyl acyl chlorides, alkyl esters or carboxylic acids to produceN-acylamino acids), N-alkyl acylamino acids, and acylated proteinhydrolysates, and mixtures thereof.

Other acids which are useful in the present invention are selected fromthe group comprising linear or branched alkylbenzene sulfonic acids,alkyl sulfuric acid esters, alkoxylated alkyl sulfuric acid esters,α-sulfonated alkyl ester acids, α-sulfonated ester diacids, alkoxylatedα-sulfonated alkyl ester acids, α-sulfonated dialkyl diester acids,di-α-sulfonated dialkyl diester acids, α-sulfonated alkyl acetate acids,primary and secondary alkyl sulfonic acids, perfluorinated alkylsulfonic acids, sulfosuccinic mono- and diester acids, polysulfosuccinicpolyester acids, sulfoitaconic diester acids, sulfosuccinamic acids,sulfosuccinic amide acids, sulfosuccinic imide acids, phthalic acids,sulfophthalic acids, sulfoisophthalic acids, phthalamic acids,sulfophthalamic acids, alkyl ketone sulfonic acids,hydroxyalkane-1-sulfonic acids, lactone sulfonic acids, sulfonic acidamides, sulfonic acid diamides, alkyl phenol sulfuric acid esters,alkoxylated alkyl phenol sulfuric acid esters, alkylated cycloalkylsulfuric acid esters, alkoxylated alkylated cycloalkyl sulfuric acidesters, dendritic polysulfonic acids, dendritic polycarboxylic acids,dendritic polyphosphoric acids, sarcosinic acids, isethionic acids, andtauric acids, and mixtures thereof.

Additionally in accordance with the present invention, suitable acids ofthe present invention include fluorinated carboxylic acids, fluorinatedsulfonic acids, fluorinated sulfate acids, fluorinated phosphonic andphosphinic acids, and mixtures thereof.

Due to their inherent hydrolytic instability, the sulfuric acid estersare preferably immediately converted to ethylenically unsaturated aminesalts. For example, linear dodecyl alcohol is sulfated with SO₃ toproduce an intermediate, hydrolytically unstable, dodecyl alcoholsulfate acid as shown in Scheme I below. The intermediate acid isneutralized with an ethylenically unsaturated nitrogenous base, such asallyl amine, to produce a dodecyl sulfate ethylenically unsaturatedamine salt.

Various polymerizable surface active agents are described in U.S. Pat.No. 5,969,032, hereby incorporated by reference herein.

Additionally, for example, methyl laurate is sulfonated with SO₃ toproduce an intermediate α-sulfonated lauryl methyl ester acid, as shownin Scheme II below. This acid is neutralized with an ethylenicallyunsaturated nitrogenous base, such as allyl amine, to produce anα-sulfonated lauryl methyl ester ethylenically unsaturated amine salt.Additionally, an α-sulfonated lauryl methyl ester ethylenicallyunsaturated amine di-salt may be produced as shown below in Scheme III.The α-sulfonated lauryl methyl ester ethylenically unsaturated aminesalt and the α-sulfonated lauryl fatty acid ethylenically unsaturatedamine di-salt may be formed as a mixture depending on the sulfonationconditions employed. The ratio of unsaturated amine salt to unsaturatedamine di-salt is readily controlled by sulfonation conditions, wellknown to those skilled in the art.

Ethylenically unsaturated amine salts of sulfosucinnate ester acids aretypically produced by sulfitation of a succinic acid alkyl diester withsodium bisulfite, followed by ionic exchange with an ethylenicallyunsaturated nitrogenous base, such as allyl amine, as shown in Scheme IVbelow.

The sarcosinic acid ethylenically unsaturated amine salts are preparedby the amidation of a fatty acid, a fatty acid alkyl ester or a fattyacid chloride with sarcosine, followed by addition of an ethylenicallyunsaturated nitrogenous base, such as allyl amine, as shown in Scheme Vbelow. Optionally, and somewhat less preferably, the ethylenicallyunsaturated nitrogenous base is combined with sarcosine to produce thecorresponding sarcosine salt, which is then be used to amidate the fattyacid, fatty acid alkyl ester or fatty acid chloride.

The isethionic acid ethylenically unsaturated amine salts may beprepared by the esterification of a fatty acid, a fatty acid alkyl esteror a fatty acid chloride with isethionic acid, followed by addition ofan ethylenically unsaturated nitrogenous base, such as allyl amine, asshown in Scheme VI below. Additionally, isethionic acid ethylenicallyunsaturated amine salts may be prepared by esterfying a fatty acid, afatty acid alkyl ester or a fatty acid chloride with the sodium salt ofisethionic, followed by ion exchange with the ethylenically unsaturatednitrogenous base, such as allyl amine. Optionally, isethionic acid, orits sodium salt, may be combined with the ethylenically unsaturatednitrogenous base, such as allyl amine, to produce the isethionic acidallyl amine salt, which may then be esterified with a fatty acid, afatty acid alkyl ester or a fatty acid chloride.

The preferred acids of the present invention are branched or linearalkylbenzene sulfonic acids, alkyl sulfuric acid esters, alkoxylatedalkyl sulfuric acid esters, α-sulfonated alkyl ester acids, fattycarboxylic acids and phosphoric acid esters, and mixtures thereof. Themost preferred acids of the present invention are branched or linearalkylbenzene sulfonic acids, alkyl sulfuric acid esters, and alkoxylatedalkyl sulfuric acid esters, and mixtures thereof.

Another object of the present invention are sulfonic acid salts ofethylenically unsaturated amines, derived from sultone precursors, suchas cyclic alkyl sultones. Examples of these sultone-derived sulfonicacid salts (e.g., allyl amine salts) include2-acetamidoalkyl-1-sulfonates and amino carboxy acid alkyl sulfonates,as shown in Scheme VII and Scheme VIII below.

In general, nitrogenous bases, which are useful in the present inventionare any nitrogenous base which contains an ethylenically unsaturatedmoiety, including various vinyl amines. In addition to allyl amine, asshown in the above schemes, other examples of nitrogenous bases that areuseful in the present invention are ethylenically unsaturated aminesselected from the group comprising vinyl amine, N-methyl N-allyl amine,C₁-C₂₄ alkyl allyl amine, C₁-C₂₄ alkyl ethoxylated and/or propoxylatedallyl amine, C₁-C₂₄ dialkyl allyl amine, ethoxylated and/or propoxylatedallyl amine diallyl amine, C₁-C₂₄ alkyl diallyl amine, ethoxylatedand/or propoxylated diallyl amine, triallyl amine, 1,2-diaminoethene,aminocrotonitrile, diaminomaleonitrile, N-allylcyclopentylamine,N-allylaniline, allylcyclohexylamine,[1-(2-allylphenoxy)-3-(isopropylamino)-2-propanol],3-amino-2-butenethioamide, bis[4-(dimethylamino)-benzylidene]acetone,1,4-butanediol bis(3-aminocrotonate), 3-amino-1-propanol vinyl ether,2-(diethylamino)ethanol vinyl ether, 4-(diethylamino)cinnamaldehyde,4-(diethylamino)cinnamonitrile, 2-(diethylamino)ethyl methacrylate,diethyl(6-methyl-2-pyridylaminomethylene)maleate,3-(dimethylmaino)acrolein, 2-(dimethylamino)ethyl methacrylate,4-dimethylaminocinnamaldehyde, 2-(dimethylamino)ethyl acrylate,3-(dimethylamino)-2-methyl-2-propenal, 9-vinylcarbazole,N-vinylcaprolactam, 1-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine,allylcyclohexylamine, N-allylcyclopentylamine,allyl(diisopropylamino)dimethylsilane, 1-allylimidazole,1-vinyl-2-pyrrolidinone, N-[3-(dimethylmaino)propyl]methacrylamide,4-[4-(dimethylamino)styryl]pyridine,2-[4-(dimethylamino)styryl]pyridine,2-[4-(1,2-diphenyl-1-butenyl)phenoxy]-N,N-dimethylethylamine,2-[4-dimethylamino)styryl]-benzothiozole,5-[4-dimethylamino)phenyl]-2,4-pentandienal,(dimethylamino-methylene)malononitrile, 4-dimethylaminocinnamonitrile,4-(dimethylamino)chalcone, [6-(3,3-dimethylallylamino-purine riboside,3,7-dimethyl-2,6-octadien-1-ylamine, 2-isopropenylaniline, isopropyl3-aminocrotonate, S-{2-[3-(hexyloxy)benzoyl]-vinyl}glutathione, methyl3-aminocrotonate, N-methylallylamine,N-methyl-1-(methylthio)-2-nitroetheneamine, oleylamine,tetrakis(dimethylamino)ethylene,5-[(6,7,8-trimethoxy-4-quinaolinyl)amino]-1-pentanol nitrate ester,tris(2-methylallyl)amine, N,N,N′,N′-tetramethyl-2-butene-1,4-diamine,S-{2-[3-(octyloxy)benzoyl]vinyl}-glutathione,4,4′-vinylidene-(N,N-dimethylaniline), 2′,5′-dimethoxy-4-stilbenamine,3-(dimethylamino)propyl acrylate, 3-dimethylaminoacrylonitrile,4-(dimethylamino)-cinnamic acid,2-amino-1-propene-1,1,3-tricarbonitrile, 2-amino-4-pentenoic acid, N,N′-diethyl-2-butene-1,4-diamine,10,11-dihyro-N,N-dimethyl-5-methylene-5H-dibenzo[a,d]-cyclohepene-10-ethanaminemaleate,4-(dicyanomethylene)-2-methyl-6-(4-dimethyl-aminostyryl)-4H-pyran,N-ethyl-2-methylallylamine, ethyl 3-aminocrotonate,ethyl-α-cyano-3-indoleacrylate, ethyl-3-amino-4,4-dicyano-3-butenoate,1,3-divinyl-1,1,3,3-tetramethyldisilazane,N-(4,5-dihydro-5-oxo-1-phenyl-1H-pyrazol-3-yl)-9-octadecen-amide, andN-oleoyl-tryptophan ethyl ester, and mixtures thereof.

More preferred nitrogenous bases of the present invention are allylamine, diallyl amine, triallyl amine, methylallyl amine, allyldimethylamine, methyl 3-amino crotonate, 3-amino crotononitrile,3-amino-1-propanol vinyl ether, N-methyl N-allyl amine,2-(dimethylamino)ethyl acrylate, or 1,4-diamino-2-butene, and mixturesthereof. The most preferred nitrogenous bases of the present inventionare allyl amine, diallyl amine, triallyl amine, methallyl amine,N-methyl N-allyl amine, and 2-(dimethylamino)ethyl acrylate, andmixtures thereof.

Accordingly, the present invention encompasses surface active agents ofthe formula:(R₁)_(n)—Ar(SO₃ ⁻M⁺)_(m)wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 1-24 carbon atoms; wherein Ar is a phenyl, polyphenyl, napthyl,polynapthyl, styryl, or polystyryl group, or a mixture thereof; whereinM⁺ is a conjugate acid of the nitrogenous base; wherein n=1-5 and m=1-8;and wherein the total number of carbon atoms represented by (R₁)_(n) isat least 5. In a preferred embodiment R₁ is a saturated or unsaturatedhydrocarbon group having from about 6-24 carbon atoms, Ar is a phenyl,M⁺ is a conjugate acid of the nitrogenous base, the nitrogenous baseselected from the group consisting of allyl amine, diallyl amine,triallyl amine, methallyl amine, N-methyl N-allyl amine or2-(dimethylamino)ethyl acrylate, and mixtures thereof and n=1 and m=1.In another preferred embodiment, the surface active agent is of theformula:

wherein n1=4-18; and wherein R′ is hydrogen or saturated or unsaturatedhydrocarbon group having from about 1-8 carbon atoms.

The present invention further encompasses surface active agents of theformula(R₁)_(n1)—{Ar(SO₃ ⁻M⁺)_(m1)}-O—{Ar(SO₃ ⁻M⁺)_(m2)}-(R₂)_(n2)wherein R₁ and R₂ are independently hydrogen, or saturated orunsaturated hydrocarbon groups having from about 1-24 carbon atoms;wherein Ar is a phenyl, polyphenyl, napthyl, polynapthyl, styryl, orpolystyryl group, or a mixture thereof; wherein M⁺ is a conjugate acidof the nitrogenous base; wherein n1 and n2 are independently 0-5,provided that n1 and n2 are not both equal to zero; and wherein m1 andm2 are independently 0-8, provided that m1 and m2 are not both equal tozero. In a preferred embodiment, R₁ is hydrogen and R₂ is a saturated orunsaturated hydrocarbon group having from about 6-24 carbon atoms, Ar isphenyl, M⁺ is a conjugate acid of the nitrogenous base, the nitrogenousbase selected from the group consisting of allyl amine, diallyl amine,triallyl amine, methallyl amine, N-methyl N-allyl amine or2-(dimethylamino)ethyl acrylate, and mixtures thereof, n1=4, n2=1, andm1 and m2 both equal one. In another preferred embodiment, R₁ and R₂ areindependently saturated or unsaturated hydrocarbon groups having fromabout 6-24 carbon atoms, Ar is phenyl, M⁺ is a conjugate acid of thenitrogenous base, the nitrogenous base selected from the groupconsisting of allyl amine, diallyl amine, triallyl amine, methallylamine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, andmixtures thereof, n1 and n2 both equal one, and m1 and m2 both equalone. In another preferred embodiment, the surface active agent is of theformula:

wherein n and n′ are independently 4-18; and wherein R′ and R″ areindependently hydrogen, methyl, ethyl or propyl.

The present invention further encompasses surface active agents of theformula:R₁—CH(SO₃ ⁻ M ⁺)CO₂R₂wherein R₁ and R₂ are independently saturated or unsaturated hydrocarbongroups having from about 1-24 carbon atoms; and wherein M⁺ is aconjugate acid of the nitrogenous base. In a preferred embodiment, R₁ isa saturated or unsaturated hydrocarbon group having from about 6-24carbon atoms, R₂ is methyl, ethyl, or propyl, or a mixture thereof, andM⁺ is a conjugate acid of the nitrogenous base, the nitrogenous baseselected from the group consisting of allyl amine, diallyl amine,triallyl amine, methallyl amine, N-methyl N-allyl amine, or2-(dimethylamino)ethyl acrylate, and mixtures thereof. In anotherpreferred embodiment, the surface active agent is of the formula:

wherein n=3-18.

The present invention further encompasses surface active agents of theformula:R₁—CH(SO₃ ⁻ M ⁺)CO₂ M ⁺wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 3-24 carbon atoms; and wherein M⁺ is a conjugate acid of thenitrogenous base. In a preferred embodiment, R₁ is a saturated orunsaturated hydrocarbon group having from about 6-24 carbon atoms, M⁺ isa conjugate acid of the nitrogenous base, the nitrogenous base selectedfrom the group consisting of allyl amine, diallyl amine, triallyl amine,methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethylacrylate, and mixtures thereof In another preferred embodiment, thesurface active agent is of the formula:

wherein n=3-18.

The present invention further encompasses surface active agents of theformula:R₁—CH(SO₃ ⁻M⁺)C(O)O(CH₂CH(R′)O)_(n)R₂wherein R₁ and R₂ are independently saturated or unsaturated hydrocarbongroups having from about 1-24 carbon atoms; wherein R′ is methyl orhydrogen; wherein n=1-100; and wherein M⁺ is a conjugate acid of thenitrogenous base. In a preferred embodiment, R₁ is a saturated orunsaturated hydrocarbon group having from about 4-24 carbon atoms, R′ ismethyl or hydrogen, R₂ is methyl, ethyl, or propyl, and mixturesthereof, M⁺ is a conjugate acid of the nitrogenous base, the nitrogenousbase selected from the group consisting of allyl amine, diallyl amine,triallyl amine, methallyl amine, N-methyl N-allyl amine, or2-(dimethylamino)ethyl acrylate, and mixtures thereof, and n=1-100. Inanother preferred embodiment, the surface active agent is of theformula:

wherein n1=2-18; and wherein n2=1-20.

The present invention further encompasses surface active agents of theformula:R₁—(SO₃ ⁻M⁺)wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 6-24 carbon atoms and wherein M⁺ is a conjugate acid of thenitrogenous base. In a preferred embodiment, R₁ is a saturated orunsaturated hydrocarbon group having from about 6-24 carbon atoms, andM⁺ is a conjugate acid of the nitrogenous base, the nitrogenous baseselected from the group consisting of allyl amine, diallyl amine,triallyl amine, methallyl amine, N-methyl N-allyl amine, or2-(dimethylamino)ethyl acrylate, and mixtures thereof. In anotherpreferred embodiment, the surface active agent is of the formula:

wherein n=5-17.

The present invention further encompasses surface active agents of theformula:R₁CO₂(CH₂)_(n)CH(SO₃ ⁻M⁺)CO₂R₂wherein R₁ and R₂ are independently saturated or unsaturated hydrocarbongroups having from about 1-24 carbon atoms; wherein n=0-10; and whereinM⁺ is a conjugate acid of the nitrogenous base. In a preferredembodiment, R₁ and R₂ are independently saturated or unsaturatedhydrocarbon groups having from about 1-24 carbon atoms, n=1-6, and M⁺ isa conjugate acid of the nitrogenous base, the nitrogenous base selectedfrom the group consisting of allyl amine, diallyl amine, triallyl amine,methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethylacrylate, and mixtures thereof In another preferred embodiment, thesurface active agent is of the formula:

wherein n1=0-17

The present invention further encompasses surface active agents of theformula:R₁CO₂(CH₂)_(n)SO₃ ⁻M⁺wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 1-24 carbon atoms; wherein n=1-10; and wherein M⁺ is a conjugateacid of the nitrogenous base. In a preferred embodiment, R₁ is asaturated or unsaturated hydrocarbon group having from about 6-24 carbonatoms, n=1-5, and M⁺ is a conjugate acid of the nitrogenous base, thenitrogenous base selected from the group consisting essentially of allylamine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allylamine, or 2-(dimethylamino)ethyl acrylate, or a mixture thereof. Inanother preferred embodiment, the surface active agent is of theformula:

wherein n1=2-18.

The present invention further encompasses surface active agents of theformula:(R₁)_(n)—Ar—O(CH₂CH(R′)O)_(m)(SO₃ ⁻M⁺)wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 1-24 carbon atoms; wherein Ar is a phenyl, polyphenyl, napthyl,polynapthyl, styryl, or polystyryl group, and mixtures thereof; whereinR′ is methyl or hydrogen; wherein M⁺ is a conjugate acid of thenitrogenous base; wherein n=1-4; wherein the total number of carbonatoms represented by (R₁)_(n) is at least 5; and wherein m=0-100. In apreferred embodiment, R₁ is a saturated or unsaturated hydrocarbon grouphaving from about 6-24 carbon atoms, Ar is phenyl; M⁺ is a conjugateacid of the nitrogenous base, the nitrogenous base selected from thegroup consisting of allyl amine, diallyl amine, triallyl amine,methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethylacrylate, and mixtures thereof, n=1, and m=0-100. In another preferredembodiment, the surface active agent is of the formula:

wherein n1=5-18; and wherein n2 =0-20.

The present invention further encompasses surface active agents of theformula:R₁O(CH₂CH(R′)O)_(n)(SO₃ ⁻M⁺)wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 1-24 carbon atoms; wherein R′ is methyl or hydrogen; whereinn=0-100; and wherein M⁺ is a conjugate acid of the nitrogenous base. Ina preferred embodiment, R₁ is a saturated or unsaturated hydrocarbongroup having from about 6-24 carbon atoms, R′ is methyl or hydrogen,n=0-100, and M⁺ is a conjugate acid of the nitrogenous base, thenitrogenous base selected from the group consisting of allyl amine,diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine,or 2-(dimethylamino)ethyl acrylate, and mixtures thereof. In anotherpreferred embodiment, the surface active agent is of the formula:

wherein n1=5-18. In another preferred embodiment, the surface activeagent is of the formula:

wherein n1=5-18; and wherein n=1-20.

The present invention further encompasses surface active agents of theformula:R₁CO₂ ⁻M⁺wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 4-24 carbon atoms; and wherein M⁺ is a conjugate acid of thenitrogenous base. In a preferred embodiment, R₁ is a saturated orunsaturated hydrocarbon group having from about 6-24 carbon atoms, andM⁺ is a conjugate acid of the nitrogenous base, the nitrogenous baseselected from the group consisting of allyl amine, diallyl amine,triallyl amine, methallyl amine, N-methyl N-allyl amine, or2-(dimethylamino)ethyl acrylate, and mixtures thereof. In anotherpreferred embodiment, the surface active agent is of the formula:

wherein n=5-18.

The present invention further encompasses surface active agents of theformula:R₁CON(R′)(CH₂)_(n)CO₂ ⁻M⁺wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 1-24 carbon atoms; wherein R′ is methyl, ethyl, propyl orhydrogen; wherein M⁺ is a conjugate acid of the nitrogenous base; andwherein n=1-10. In a preferred embodiment, M⁺ is a conjugate acid of thenitrogenous base, the nitrogenous base selected from the groupconsisting of allyl amine, diallyl amine, triallyl amine, methallylamine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, andmixtures thereof, R′ is methyl, ethyl, propyl or hydrogen, and n=2-5. Inanother preferred embodiment, the surface active agent is of theformula:

wherein n1=2-18.

The present invention further encompasses surface active agents of theformula:R₁CON(R′)(CH₂)_(n)SO₃M⁻wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 1-24 carbon atoms; wherein R′ is methyl, ethyl, propyl orhydrogen; wherein M⁺ is a conjugate acid of the nitrogenous base; andwherein n=1-10. In a preferred embodiment, M⁺ is a conjugate acid of thenitrogenous base, the nitrogenous base selected from the groupconsisting of allyl amine, diallyl amine, triallyl amine, methallylamine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, andmixtures thereof, R′ is methyl, ethyl, propyl or hydrogen, and n=2-5. Inanother preferred embodiment, the surface active agent is of theformula:

wherein n1=2-18.

The present invention further encompasses surface active agents of theformula:R₁O(CH₂CH(R′)O)_(n)COCH₂SO₃ ⁻M⁺wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 1-24 carbon atoms; wherein R′ is methyl or hydrogen; whereinn=0-100; wherein M⁺ is a conjugate acid of the nitrogenous base. In apreferred embodiment, R₁ is a saturated or unsaturated hydrocarbon grouphaving from about 6-24 carbon atoms; R′ is methyl or hydrogen, M⁺ is aconjugate acid of the nitrogenous base, the nitrogenous base selectedfrom the group consisting of allyl amine, diallyl amine, triallyl amine,methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethylacrylate, and mixtures thereof; and n=0-100. In another preferredembodiment, the surface active agent is of the formula:

wherein n1=5-17; and wherein n=0-20.

The present invention further encompasses surface active agents of theformula:

wherein R₄ is an alkyl group having 1 to 20 carbon atoms: n is aninteger from 2 to 15; and X⁺ is selected from the group consisting ofNH₃ ⁺,NH₂R₆ and NR₆R₇ wherein R₆ and R₇ are independently C₁- C₄alkyl orhydroxyalkyl groups. The present invention further encompasses surfaceactive agents wherein the allyl amine salt of alkyl ether sulfate is anallyl amine salt of laureth sulfate.

The present invention further encompasses surface active agents of theformula:R₁O(PO₃)^(x−)M⁺ _(y)wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 1-24 carbon atoms, phenyl, polyphenyl, napthyl, polynapthyl,styryl, or polystyryl group, an alkyl/alkoxylate substituted phenyl, analkyl/alkoxylate substituted or poly-substituted polyphenyl, analkyl/alkoxylate substituted or poly-substituted napthyl, analkyl/alkoxylate substituted or poly-substituted polynapthyl, analkyl/alkoxylate substituted or poly-substituted styryl, or analkyl/alkoxylate substituted or poly-substituted polystyryl group, andmixtures thereof; wherein M⁺ is a conjugate acid of the nitrogenousbase; wherein x=1 or 2; and wherein y=1 or 2.

The present invention further encompasses surface active agents of theformula:[R₁O(CH₂CH(R′)O)_(m)]_(n)P(O)_(p) ^(x−)M⁺ _(y)wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 1-24 carbon atoms; wherein R′ is methyl or hydrogen; wherein M⁺ isa conjugate acid of the nitrogenous base, the nitrogenous base selectedfrom the group consisting of allyl amine, diallyl amine, triallyl amine,methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethylacrylate, and mixtures thereof; m=0-100; wherein n=1 or 2; wherein p=2or 3; wherein x=1 or 2; and wherein y=1 or 2.

The present invention further encompasses surface active agents of theformula:[(R₁)_(n)ArO(CH₂CH(R′)O)_(m)]_(q)P(O)_(p) ^(x−)M⁺ _(y)wherein R₁ is a saturated or unsaturated hydrocarbon group having fromabout 1-24 carbon atoms; wherein Ar is phenyl; wherein R′ is methyl orhydrogen; wherein M⁺ is a conjugate acid of the nitrogenous base, thenitrogenous base selected from the group consisting of allyl amine,diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine,or 2-(dimethylamino)ethyl acrylate, and mixtures thereof; wherein n=1-4;wherein m=0-100; wherein q=1 or 2; wherein p=2 or 3; wherein x=1 or 2;and wherein y=1 or 2.

The present invention further encompasses surface active agents of theformula:

wherein R₅ is an alkyl group having 1 to 20 carbon atoms; n is aninteger from 2 to 15; and X⁺ is selected from the group consisting ofNH₃ ⁺, NH₂R₆ and NR₆R₇ wherein R₆ and R₇ are independently C₁-C₄ alkylor hydroxyalkyl groups. The present invention further encompassessurface active agents wherein the allyl amine salt of a phosphate esteris an allyl amine salt of nonyl phenol ethoxylate phosphate ester.

The present invention further encompasses surface active agents that areallyl amine salts, wherein the allyl amine salt is an allyl amine saltof an alkyl half ester of the α, β-ethylenically unsaturated C₄-C₈dicarboxylic acids, and combinations thereof.

The present invention further encompasses polymerizable surface activeagents which are quaternary ammounium salts of the general formula:

wherein R₁, R₂, R₃, and R₄ are independently, substituted orunsubstituted hydrocarbyl groups of from about 1 to about 30 carbonatoms, or hydrocarbyl groups having from about 1 to about 30 carbonatoms and containing one or more aromatic, ether, ester, amido, or aminomoieties present as substituents or as linkages in the radical chain,wherein at least one of the R₁-R₄ groups contains at least one or moreethenylene groups; and wherein X⁻ is an anion group selected from thegroup consisting of sulfonate, sulfate, sulfinate, sulfenate, phosphate,carboxylate, nitrate, and acetate. Polymerizable surface active agentsof the present invention include those of the above general formula inthe form of ring structures formed by covalently linking two of theR₁-R₄ groups. Examples include unsaturated imidazolines, imidazoliniums,and pyridiniums, and the like.

The disclosures of all documents, e.g., patents and journal articles,cited above or below are hereby incorporated by reference in theirentirety.

In the following examples, all amounts are stated in percent by weightof active material unless indicated otherwise. One skilled in the artwill recognize that modifications may be made in the present inventionwithout deviating from the spirit or scope of the invention. Theinvention is illustrated further by the following examples which are notto be construed as limiting the invention or scope of the specificprocedures or compositions described herein. As used in the examplesappearing below, the following designations, symbols, terms andabbreviations have the indicated meanings:

Material Definition Polystep ® A-13 Linear dodecylbenzene sulfonic acid(commercially available from Stepan Company, Northfield Illinois)Polystep ® A-16 Branched dodecylbenzene sulfonic acid, sodium salt(commercially available from Stepan Company, Northfield Illinois)Polystep ® A-17 Branched dodecylbenzene sulfonic acid (commerciallyavailable from Stepan Company, Northfield Illinois) Cedephos CP-610Nonyl Phenol 9-EO Phosphoric Acid Ester (commercially available fromStepan Company, Northfield Illinois)

Procedures

Due to their amphiphilic character, surfactants have a tendency toadsorb at various liquid-liquid interfaces, which leads to a reductionof surface or interfacial tension. After saturating an interface, thesesurface active molecules begin to aggregate in the solution to formmicelles at a specific surfactant concentration known as the criticalmicelle concentration (CMC). The adsorption characteristics and themicellization behavior of surfactants are responsible for thetechnologically important properties of surfactants, such as foaming,detergency, wetting, solubilization, emulsification, and the like. Thus,the efficiency of any surface active agent relates to its ability tolower interfacial tension, form micelles, and display favorableadsorption characteristics by providing efficient packing of the surfaceactive molecules at the interface in a very small concentration.

The following test procedures were used to evaluate the ethylenicallyunsaturated amine salts of the present invention. A fully automatedKruss K-12 tensiometer was used to measure the adsorption and micellarbehavior of the polymerizable, surface active agents. All of themeasurements were done at room temperature, and distilled water was usedfor CMC measurements. Interfacial tension between a 0.3% activesurfactant solutions and mineral oil was measured using a spinning droptensiometer as developed by the University of Texas.

All ¹H NMR spectra were recorded using a 270 MHz Joel Delta NMR FourierTransform Spectrometer. Chemical shifts (δ) are reported in parts permillion (ppm) down field from tetramethylsilane (TMS) using internal TMSor residual non-deuterated solvent as a reference. Multiplicity isindicated by the following abbreviations: singlet (s), doublet (d),triplet (t), quartet (q), heptet (h), multiplet (m), broad multiplet (brm) doublet of doublets (dd), etc. All samples were isolated in solidform by oven-drying aqueous solution of the surface active agents toremove substantially all water from the sample; NMR data for all sampleswas acquired by dissolving the solid sample in CD₃OD.

EXAMPLE #1

Approximately 7.5 ml of allyl amine and about 150.0 g of deionized waterwere charged to a reaction vessel equipped with a means for agitationand a means for cooling. The allyl amine/water mixture temperature wasadjusted to about 25° C. and approximately 32.5 g of Polystep® A-13 wasadded, to give the desired ethylenically unsaturated amine salt as anapproximately 20% active aqueous solution with a pH of about 6.5. The pHof the resulting salt solution may be adjusted as needed with theaddition of more acid or amine; higher and lower pH materials may beproduced as desired. ¹H NMR: δ 7.8 (m, 2H), 7.2 (m, 2H), 6.0 (m, 1H),5.4 (ddt, 2H), 5.0 (br, 3H), 3.6 (m, 2H), 1.7 (bm, 3H), 1.3 (bm, 16H),0.9 (m, 6H). The CMC, Surface Tension Reduction, and Effectiveness ofSurfactant are reported in Table I.

EXAMPLE #2

Approximately 7.5 ml of allyl amine and about 150.0 g of deionized waterwere charged to a reaction vessel equipped with a means for agitationand a means for cooling. The allyl amine/water mixture temperature wasadjusted to about 25° C. and approximately 32.5 g of Polystep® A-17 wasadded, to give the desired ethylenically unsaturated amine salt as anapproximately 20% active aqueous solution with a pH of about 7.0. The pHof the resulting salt solution may be adjusted as needed with theaddition of more acid or amine; higher and lower pH materials may beproduced as desired. ¹H NMR: δ 7.8 (m, 2H), 7.4 (bt, 2H), 5.9 (ddt, 1H),5.4 (m, 2H), 4.9 (br, 3H), 3.5 (dd, 2H), 2.9 (m, 1H), 1.6 (m, 3H),0.9-1.1 (m, 28H).

EXAMPLE #3

Approximately 12.3 ml of diallyl amine and about 170.0 g of deionizedwater were charged to a reaction vessel equipped with a means foragitation and a means for cooling. The diallyl amine/water mixturetemperature was adjusted to about 25° C. and approximately 32.5 g ofPolystep® A-13 was added, to give the desired ethylenically unsaturatedamine salt as an approximately 20% active aqueous solution with a pH ofabout 7.0. The pH of the resulting salt solution may be adjusted asneeded with the addition of more acid or amine; higher and lower pHmaterials may be produced as desired. ¹H NMR: δ 7.8 (m, 2H), 7.2 (m,2H), 6.0 (m, 2H), 5.4 (m, 4H), 5.0 (br, 2H), 3.6 (m, 4H), 1.7 (bm, 4H),1.3 (bm, 15H), 0.9 (bm, 6H).

EXAMPLE #4

Approximately 12.3 ml of diallyl amine and about 170.0 g of deionizedwater were charged to a reaction vessel equipped with a means foragitation and a means for cooling. The allyl amine/water mixturetemperature was adjusted to about 25° C. and approximately 32.5 g ofPolystep® A-17 was added, to give the desired ethylenically unsaturatedamine salt as an approximately 20% active aqueous solution with a pH ofabout 7.0. The pH of the resulting salt solution may be adjusted asneeded with the addition of more acid or amine; higher and lower pHmaterials may be produced as desired. ¹H NMR: δ 7.8 (m, 2H), 7.5 (m,2H), 5.9 (m, 2H), 5.4 (m, 4H), 4.9 (brs, 2H), 3.6 (m, 4H), 2.8 (m, 1H),1.7 (bm, 3H), 0.9-1.1 (m, 28H).

EXAMPLE #5 Comparative Example

Approximately 13.7 ml of propyl amine and about 170.0 g of deionizedwater were charged to a reaction vessel equipped with a means foragitation and a means for cooling. The propyl amine/water mixturetemperature was adjusted to about 25° C. and approximately 32.5 g ofPolystep® A-13 was added, to give the saturated amine salt as anapproximately 20% active aqueous solution with a pH of about 7.0. The pHof the resulting salt solution may be adjusted as needed with theaddition of more acid or amine; higher and lower pH materials may beproduced as desired. ¹H NMR: δ 7.8 (dd, 2H0, 7.23 (t, 2H), 4.9 (br, 2H),2.85 (t, 2H), 1.6 (m, 6H), 1.2 (m, 14H), 0.9 (m, 6H). The CMC, SurfaceTension Reduction, and Effectiveness of the Surfactant are reported inTable I.

EXAMPLE #6

Approximately 30.0 ml of allyl amine and about 408.0 g of deionizedwater were charged to a reaction vessel equipped with a means foragitation and a means for cooling. The allyl amine/water mixturetemperature was adjusted to about 25° C. and approximately 80.0 g oflauric acid was added, to give the desired ethylenically unsaturatedamine salt as an approximately 20% active aqueous solution with a pH ofabout 7.0. (The carboxylic acid may be a solid at room temperature andcan be pre-melted prior to addition to the amine/water mixture, for easeof handling. As an alternative, the carboxylic acid and water may becombined and heated to produce a uniform mixture, i.e., 50-60° C. forlauric acid, followed by addition of the unsaturated amine). The pH ofthe resulting salt solution may be adjusted as needed with the additionof more acid or amine; higher and lower pH materials may be produced asdesired. ¹H NMR: δ 6.0 (m, 1H), 5.5 (ddt, 2H), 3.6 (m, 2H), 2.3 (t, 2H),1.6 (br, 2H), 1.42 (s, 5H, residual water), 1.41 (s, 3H), 1.4 (br, 18H),0.9 (t, 3H).

EXAMPLE #7 Comparative Example

Approximately 16.4 ml of propyl amine and about 210.0 g of deionizedwater were charged to a reaction vessel equipped with a means foragitation and a means for cooling. The propyl amine/water mixturetemperature was adjusted to about 25° C. and approximately 40.0 g oflauric acid was added, to give the saturated amine salt as anapproximately 20% active aqueous solution with a pH of about 7.0. (Thecarboxylic acid may be a solid at room temperature and can be pre-meltedprior to addition to the amine/water mixture, for ease of handling. Asan alternative, the carboxylic acid and water may be combined and heatedto produce a uniform mixture, i.e., 50-60° C. for lauric acid, followedby addition of the saturated amine). The pH of the resulting saltsolution may be adjusted as needed with the addition of more acid oramine; higher and lower pH materials may be produced as desired. ¹H NMR:δ 5.0 (s, 3H), 3.3 (p, 2H), 2.8 (dt, 2H), 2.25 (t, 2H), 1.6 (m, 2H), 1.3(m, 17H), 1.0 (t, 3H), 0.9 (t, 3H).

EXAMPLE #8

Approximately 5.1 ml of allyl amine and about 320.0 g of deionized waterwere charged to a reaction vessel equipped with a means for agitationand a means for cooling. The allyl amine/water mixture temperature wasadjusted to about 25° C. and approximately 75.0 g of CP-610 was added,to give the desired unsaturated amine salt as an approximately 20%active aqueous solution with a pH of about 7.0. (The phosphoric acidester may be a solid at room temperature and can be pre-melted prior toaddition to the amine/water mixture, for ease of handling. As analternative, the phosphoric acid ester and water may be combined andheated to produce a uniform mixture, followed by addition of theunsaturated amine). The pH of the resulting salt solution may beadjusted as needed with the addition of more acid or amine; higher andlower pH materials may be produced as desired. ¹H NMR: δ 7.2 (m, 2H),6.8 (m, 2H), 6.0 (m, 1H), 5.4 (m, 2H), 4.1 (m, 2H), 3.8 (m, 2H), 3.6 (m,32H), 0.4-1.8 (m, 19H). The CMC, Surface Tension Reduction, andEffectiveness of the Surfactant are reported in Table I.

EXAMPLE #9 Comparative Example

Approximately 5.1 ml of propyl amine and about 320.0 g of deionizedwater were charged to a reaction vessel equipped with a means foragitation and a means for cooling. The allyl amine/water mixturetemperature was adjusted to about 25° C. and approximately 75.0 g ofCP-610 was added, to give the desired unsaturated amine salt as anapproximately 20% active aqueous solution with a pH of about 7.0. (Thephosphoric acid ester may be a solid at room temperature and can bepre-melted prior to addition to the amine/water mixture, for ease ofhandling. As an alternative, the phosphoric acid ester and water may becombined and heated to produce a uniform mixture, followed by additionof the unsaturated amine). The pH of the resulting salt solution may beadjusted as needed with the addition of more acid or amine; higher andlower pH materials may be produced as desired. ¹H NMR: δ 7.2 (m, 2H),6.8 (m, 2H), 4.9 (s, 3H), 4.1 (m, 2H), 3.8 (m, 2H), 3.6 (m, 32H), 3.3(t, 2H), 2.9 (dt, 2H), 0.4-1.8 (m, 22H). The CMC, Surface TensionReduction, and Effectiveness of the Surfactant are reported in Table I.

TABLE I Surface Tension Data for Ethylenically Unsaturated Amine Saltsof Sulfonic Acids, Carboxylic Acids and Phosphoric Acid Esters,Including Comparative Examples Effectiveness of Surface EthylenicallyUnsaturated Amine Surface Tension Tension Reduction Example # Salt CMC(mg/l) at CMC (mN/m) at CMC (mN/m) 1 Allylamine Salt of 100.5 33.2 39.1Dodecylbenzene Sulfonic Acid 5 (comparative) Propylamine Salt of 480.531.0 41.3 Dodecylbenzene Sulfonic Acid Polystep ® Sodium Salt ofDodecylbenzene 156.0 35.0 37.3 A-16 Sulfonic Acid 8 Allylamine Salt ofNonylphenol 31.8 30.0 42.3 9-EO Phosphoric Acid Ester 9 (comparative)Propylamine Salt of Nonylphenol 74 31.5 40.8 9-EO Phosphoric Acid Ester

EXAMPLE #10 Emulsion Polymerization With Polystep A-17 Allyl Amine Salt

An emulsion polymerization kettle equipped with a nitrogen inlet, aheating means, and an agitation means, is charged with 250 g of waterand 8.13 g of Polystep A-17 allyl amine salt. The mixture is heated toapproximately 85° C. Approximately 17 g of a 4% aqueous ammoniumpersulfate solution (i.e. initiator solution) is added and approximately75 g of monomer solution is added while mixing, the monomer solutioncomprising 48% butyl acrylate, 49% methyl methacrylate and 3%methacrylic acid. After mixing for 15 minutes, 298 g of monomer solutionis added over 2.5 hours. After monomer solution addition is complete, 67g of initiator solution and 75 g of Polystep A-17 allyl amine salt, in35 g of water, are added separately and concurrently, over 2 hours. Theresulting mixture is agitated at 85° C. for another hour followed bydischarging the reactor to give an all acrylic latex with the followingproperties: Viscosity: 50 centipoise; pH: 6.4; Solids: 45.6(actual),46.7(theoretical); Particle Size: 115.

From the foregoing, it will be appreciated that although specificembodiments of the invention have been described herein for purposes ofillustration, various embodiments may be made without deviating from thespirit or scope of the invention.

1. A polymerizable surface active agent of the formula: R₁O(CH₂CH(R′)O)_(n)(SO₃ ⁻M⁺) wherein R₁ is a saturated or unsaturated hydrocarbon group having from about 1-24 carbon atoms; R′ is methyl or hydrogen; n=1-100; and M⁺ is a conjugate acid of a nitrogenous compound selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine and 2-(dimethylamino) ethyl acrylate and mixtures thereof.
 2. The polymerizable surface active agent according to claim 1 wherein R′ is hydrogen.
 3. The polymerizable surface active agent according to claim 1 wherein n is 1 to
 20. 4. The polymerizable surface active agent according to claim 1 wherein R′ is hydrogen, n is 1 to 20 and the nitrogenous compound is allyl amine. 